ABSTRACT
Pure hydrophobic ionic liquids are known to extract metallic species from aqueous solutions. In this work we have systematically investigated thallium (Tl) extraction from aqueous hydrochloric acid (HCl) solutions into six pure fluorinated ionic liquids, namely imidazolium- and pyrrolidinium-based ionic liquids with bis(trifluoromethanesulfonyl)imide and bis(fluorosulfonyl)-imide anions. The dependence of the Tl extraction efficiency on the structure and composition of the ionic liquid ions, metal oxidation state, and initial metal and aqueous acid concentrations have been studied. Tl concentrations were on the order of picomolar (analyzed using radioactive tracers) and millimolar (analyzed using inductively coupled plasma mass spectrometry). The extraction of the cationic thallium species Tl(+) is higher for ionic liquids with more hydrophilic cations, while for the TlX(z)(3-z) anionic species (where X = Cl(-) and/or Br(-)), the extraction efficiency is greater for ionic liquids with more hydrophobic cations. The highest distribution value of Tl(III) was approximately 2000. An improved mathematical model based on ion exchange and ion pair formation mechanisms has been developed to describe the coextraction of two different anionic species, and the relative contributions of each mechanism have been determined.
ABSTRACT
Uniaxially anisotropic chitin-silica nanocomposite solids have been obtained thanks to the electric field-induced macroscopic alignment of liquid-crystalline reactive cosuspensions. We demonstrate how chitin nanorods (260 nm long, 23 nm thick) can be aligned upon the application of an alternating current (ac) electric field, and within water-ethanol suspensions containing reactive siloxane oligomers (D(h) â¼ 3 nm). The alignment at the millimeter length scale is monitored by in situ small-angle X-ray scattering (SAXS) and polarized light optical microscopy. The composition and state (isotropic, chiral nematic) of the cosuspensions are proven to be determining factors. For nematic phases, the alignment is preserved when the electric field is switched off. Further solvent evaporation induces sol-gel transition, and uniaxially anisotropic chitin-silica nanocomposites are formed after complete drying of the aligned nematic suspensions. Here, the collective response of colloidal mesophases to external electric fields and the subsequent formation of ordered nanocomposite solids would represent a new opportunity for materials design.
ABSTRACT
Mesoporous silica-titania materials of tunable composition and texture, which present a high catalytic activity in the mild oxidation of sulfur compounds, have been obtained by combining the spray-drying process with the colloidal self-assembly of α-chitin nanorods (biopolymer acting as a template) and organometallic oligomers.